Deionization apparatus having non-sacrificial electrodes of different types

ABSTRACT

An apparatus for deionization of a liquid is disclosed. The apparatus has a number of deionization cells, each cell having two different types of electrodes. The first type of electrode is formed from a high surface area absorptive material (&#34;HSAAM electrode&#34;) made from resorcinol, formaldehyde, a carbon reinforcing agent, a catalyst, and reaction products thereof, and is in a carbonized form. This electrode removes ions when an electric current is applied. The second type of electrode, which does not remove ions, is formed from a non-HSAAM material. Each deionization cell has a single HSAAM electrode bordered on either side by a non-HSAAM electrode, and adjacent deionization cells do not share any electrodes of either type. The non-HSAAM electrodes are formed from carbon cloth or carbon felt fixed to one side of a plexiglass sheet, and two such sheets are needed to form a cell. The other side of each of these sheets is also provided with a carbon cloth, or carbon felt electrode, electrically isolated from that fixed to the first side. A method of making the HSAAM electrodes for the apparatus is also disclosed. The HSAAM electrodes are formed from setting a polymerized mixture of resorcinol, formaldehyde and a carbon reinforcing agent supplied in the form of carbon fibers, carbon felt or cellulose under controlled temperature and time constraints, and subsequently firing the resulting product so as to carbonize the electrode. The resulting electrodes are of a sufficient thickness to support their own weight when placed on end.

BACKGROUND OF THE INVENTION

The present invention relates to carbon aerogels, electrochemical cellsand systems for deionization and purification of water effluents.

Resorcinol is a well-known material commonly used in resins, dyes,adhesives, pharmaceuticals, and other applications. It can be obtainedin a variety of grades and forms, such as crystals, flakes, pellets, andthe like. Resorcinol, in its various forms, is soluble in water,alcohol, ether, benzene, glycerol and formaldehyde.

As disclosed in U.S. Pat. No. 5,425,858 to Farmer, resorcinol can beused to synthesize carbon aerogels. Specifically, carbon aerogel can beproduced by the polycondensation of resorcinol and formaldehyde in aslightly basic medium, followed by supercritical drying and pyrolysis inan inert atmosphere. Thin electrodes formed from such carbon aerogelsmay be used in capacitive deionization applications, as disclosed inthis reference, whose contents are incorporated by reference in theirentirety.

The thin electrode plates (approximately 0.25 mm thickness) formed bythis process, however, have a number of drawbacks. First, they areprohibitively expensive to use on a commercial scale, costing on theorder of $1000/square inch of surface area. Second, a device using theseelectrodes has only been effectively driven at voltages and currentslower than those at which water is electrolyzed. Also, the thin natureof the plates limits the deionization capacity. The thin plates are notself supporting and it is difficult to make a direct reliable electricalconnection with these. Finally, these electrodes are glued to a titaniumplate and so one of each of these plates is unavailable for use as adeionization surface.

SUMMARY OF THE INVENTION

The present invention is directed to a deionization apparatus comprisinga tank having a plurality of deionization cells. Each deionization cellcomprises three non-sacrificial electrodes of two different types. Oneelectrode comprises a high surface area absorptive material ("HSAAMelectrode") formed as a plate having two sides facing in oppositedirections. The HSAAM electrode removes ions from the liquid beingdeionized. This HSAAM electrode is bordered by two electrodes, one oneither side, which do not remove ions from the liquid being deionized.

The bottom of the tank may be provided with a network of pipes forconducting air, each pipe being provided with small holes through whichair may escape. Air pumped through these pipes agitates and mixes theliquid being deionized, thus promoting the contact and capture of ionson the HSAAM electrodes.

The non-HSAAM electrodes in the present invention are present in theform of carbon cloth (CC) or graphite plate electrodes affixed to eitherside of a flat, nonconductive structural support member. The non-HSAAMelectrode on one side of the structural support member is electricallyisolated from the non-HSAAM electrode on the other side of thestructural support member. Thus, each non-HSAAM electrode is associatedwith a different HSAAM electrode. This results in a deionization cellcomprising first and second non-HSAAM electrodes, each mounted on adifferent structural support member, but facing the same HSAAM electrodesandwiched therebetween.

The HSAAM electrodes used in the deionization cells are produced byfirst dissolving resorcinol in formaldehyde to form an initial liquor. Acatalyst is added to promote polymerization and to effect the finalstructure of the HSAAM. A predetermined amount of a non-sacrificialmaterial is introduced to the liquor as a reinforcing material.Sufficient heat is added by heating the mixture at a sufficienttemperature or for a sufficient time such that a controlledpolymerization takes place and the mixture reaches a consistencysufficient to support the reinforcing material. The resulting viscousliquid is then allowed to continue polymerization to form a solid in amold. The resulting brick is then fired in an oven until it iscarbonized, after which it is machined for subsequent use in theapparatus.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects, and advantages of the presentinvention can be seen in the drawings in which:

FIG. 1 is a perspective view of an apparatus formed in accordance withthe present invention.

FIG. 2A is a view of the tank used in the apparatus of the presentinvention. FIGS. 2B and 2C show two arrangements for immobilizing theHSAAM plates within the tank.

FIG. 3 is a top view of the apparatus of FIG. 1 arranged for serpentineflow.

FIGS. 4a and 4b show a deionization cell formed from neighboringelectrodes;

FIG. 5 shows an apparatus with three serially connected devices.

FIGS. 6A and 6B show alternatives to having all the electrodes parallelto one another.

FIG. 7 presents a top view of a tank having ion exit holes formedtherein.

FIG. 8 shows an experimental apparatus constructed along the lines ofthat shown in FIG. 5.

FIGS. 9A-9E present batch processing results using the apparatus of FIG.8.

FIG. 10 present an block diagram for an automated deionizationapparatus.

DESCRIPTION OF THE PREFERRED EMBODIMENT

FIG. 1 shows an apparatus 18 made in accordance with the presentinvention. The apparatus comprises a number of parallely arranged,upstanding electrodes 20, 22. As discussed below, two different types ofelectrodes are provided, and these alternate.

The electrodes of the apparatus are mounted widthwise in a substantiallyrectangular chamber or tank 24. The tank itself comprises a pair of sidewalls 26, 28, a pair of end walls 30, 32, and a flat bottom 34. The tankwalls are preferably formed from glass, plastic, plexiglass, or otherelectrically insulative, water-tight material.

An inlet 36 formed in the bottom and an outlet 38 in a first end wallprovide for the entry and exit of a liquid that is deionized while inthe tank. Alternatively, the inlet may be formed in the second end wallwhen serpentine flow, as depicted by the dashed path in FIG. 3, isdesired. Also, multiple inlets and outlets, spaced apart from oneanother in the bottom, or sides, may be provided when a single tank isemployed to deionize liquids from different sources, each liquid havingions of different polarities and sizes to be removed.

At the base of the tank is an air diffuser 42 through which air isintroduced. As shown in FIG. 2A, the air diffuser comprises a number ofparallely arranged pipes 44 formed from styrene or the like and havesmall openings formed therein. The pipes 44 extend across the width ofthe tank, and, in the preferred embodiment, are placed between facingelectrodes. When the apparatus is operational, air is pumped throughthese pipes to aerate and agitate the liquid in the tank. This promotesdeionization by mixing the liquid within the tank and agitating the ionsbetween oppositely charged electrodes.

It should be evident to one skilled in the art that equivalent aerationmeans may be used in place of the network of parallel tubes providedwith openings. For example, a false bottom may be provided and air,pumped between the tank bottom and false bottom, would percolate throughopenings formed in the latter. Another alternative is to place asubstantially flat plastic bladder on the tank bottom and air, oncepumped into the bladder, could enter the liquid through openings in atop side thereof.

The side walls 26, 28 of the tank are provided with a row of mountingclips, also molded from styrene or other plastic, on their inward facingsurfaces. The mounting clips 46, 48, as shown on FIG. 2a, serve to alignand retain electrodes inserted into the tank. Mounting clips 46 and 48may differ in size, shape and materials, depending on the physical andchemical properties of the electrodes 20, 22, which they are designed toaccommodate.

An electrode may be inserted, at each side edge thereof, directly intoopposing mounting clips. In such case, the electrode may be formed withan opening 50, as shown in FIG. 3, adjacent to where it is inserted intothe mounting clip. This opening 50 serves as a passage through whichliquid may pass as it courses through the tank.

Alternatively, an electrode may be indirectly held by a mounting clipvia an acrylic spacer 52 on one or both of its ends, the acrylic spacerbeing fixed to the electrode by means of a connecting clip 54. In suchcase, an opening 56 may be formed in the acrylic spacer itself to allowliquid to pass therethrough. This arrangement is especially advantageouswhen the opening cannot be formed in the electrode itself, forstructural, electrical, or other reasons.

In addition, the bottom 34 of the tank can be provided with plasticguard members 57, as seen in FIG. 2B, or grooves 58, as seen in FIG. 2Cwhich extend widthwise across the tank. Such guard members and groovesallow one to selectively, slideably adjust electrodes towards one sidewall or the other. This is especially advantageous when it is desired tohave serpentine flow of the liquid past each face of each electrode,from the inlet at one end wall of the tank to the outlet formed at theopposite end wall. As an alternative to a guard member or a groove alongwhich an electrode may slide, a central portion of the bottom wall maybe provided with slots into which upstanding bottom clips orspring-loaded retainers are inserted. The bottom edge of an electrodemay then be inserted into these bottom clips or retainers at any desireddistance from either side wall. As described above, acrylic spacer barsmay be used to bridge the gap between the free edge of the electrode andthe mounting clip.

A busbar 60 may be provided on the exterior side walls of the tank. Eachbusbar is provided with a plurality of terminals 62 electricallyisolated from one another, each one arranged to be connected to anassociated electrode. This allows one to individually control thevoltage, and the current, applied to each electrode. The individualterminals can be electrically connected to their associated electrodeswith conventional electrical leads such as alligator clips or equivalentconnecting means. More preferably, however, the individual terminals maybe connected, by means of a copper wire 64 connected via anon-sacrificial graphite rod to either the corresponding mounting clipsor, when used, the corresponding connecting clip. The electrode thencontacts the graphite rod when the electrode is inserted into themounting or connecting clip. To facilitate this electrical contact, aleaf spring, or the like, may be affixed to the end of the conductivestrip, in a known manner. The leaf spring can then be secured to thechannel of the clip in which the electrode's edge is inserted.

As stated above, two types of conductive, non-sacrificial electrodes areused in an apparatus formed in accordance with the present invention. Inthe preferred embodiment, a first type of electrode, formed as a flatplate is bordered on either of its sides by a second type of electrode.Together, the three electrodes form a deionization cell. Duringoperation, a substantially similar voltage potential is normallyestablished between an electrode of the first type and each of theelectrodes of the second type. This is accomplished by connecting onelead of a voltage source to the electrode of the first type and a pairof common leads from that same voltage source to each of the twoelectrodes of the second type. The common leads ensure that asubstantially similar potential is maintained between the electrode ofthe first type and each of the electrodes of the second type borderingthe electrode of the first type.

The first type of electrode (22) is formed from a carbon based highsurface area absorptive material ("HSAAM electrode"). This electroderemoves and retains ions from an aqueous solution when an electricalcurrent is applied. In the preferred embodiment, the HSAAM electrode isformed from resorcinol, formaldehyde, at least one of carbon fiber,carbon felt and cellulose, a catalyst, and reaction products thereof, ina carbonized form. The process for forming an HSAAM electrode isdescribed further below.

The second type of electrode (20), though formed from a conductivematerial, does not remove or retain ions when an electric current isapplied and so is non-absorptive ("non-HSAAM electrode"). This propertyis common to electrodes formed from carbon cloth, graphite, gold,platinum, and other conductive materials which do not degrade in anelectric field in an aqueous solution. In the preferred embodiment, thenon-HSAAM carbon electrode is formed from either graphite, or morepreferably from carbon cloth, such as part no. PANEX 30 woven fibersavailable from Zoltek.

As shown in FIG. 4a, the non-HSAAM carbon electrode 20 is formed as adual electrode in that it has a pair of conductive surfaces which areelectrically isolated from one another. The dual electrode 20 is formedby fixing a separate piece of carbon cloth 72a, 72b to either side of a3/8" thick sheet of plexiglass 74. The plexiglass serves as anonconductive, structurally rigid support member, and also prevents theflow of liquid directly through both pieces of carbon cloth. Thus,glass, acrylics, and the like may be used in place of plexiglass. In thepreferred embodiment, the carbon cloth is secured to either side of theplexiglass sheet by means of an epoxy adhesive. As is known to thoseskilled in the art, other adhesives, and even mechanical securing meanssuch as screws, clips, and the like may be used to secure the carboncloth (CC) electrode.

Once secured to either side of the plexiglass sheet 74, the carbon cloth72a on one side may, if desired, be electrically connected to itscounterpart 72b on the other side of the same sheet 74. Usually,however, this is not the case, so that one may apply different voltagesto the carbon cloth on each side of the plexiglass, by means of separatevoltage sources. In such case, adjacent cells within a single tank maybe driven by different voltage sources.

As shown in FIG. 4b, in an apparatus of the present invention, thesetwo-sided non-HSAAM electrodes 20 are alternated in the tank with theHSAAM electrodes 22, to each of which only a single voltage may beapplied at any given time. Thus, in an apparatus of the presentinvention, one side of an HSAAM electrode faces a CC electrode 72baffixed to a first sheet 74 of plexiglass, while the second, reverseside of the HSAAM electrode, faces a CC electrode 76a affixed to asecond sheet 78 of plexiglass. In this manner, each of the HSAAMelectrodes 22 with its pair of corresponding non-HSAAM cloth electrodesform a deionization cell 80. End walls 30, 32 have a carbon clothelectrode affixed on their inwardly facing sides, which electrodebecomes part of a cell.

In use, two CC electrodes 72b, 76a which face the same HSAAM electrode22 are usually maintained at the same polarity and voltage level.Alternatively, if desired, they can be maintained at different levels,as each is provided with its own terminal 62 on the busbar 60. Whenvoltage is applied between the HSAAM electrode 22, and its correspondingnon-HSAAM electrodes 72b, 76a, the cell 80 is activated and deionizationtakes place on both sides of the HSAAM electrode 22. Preferably, thesame voltage level is applied to both non-HSAAM electrodes of a singlecell. If, however, the two non-HSAAM electrodes on either side of anHSAAM electrode have different surface areas and so can sustaindifferent current densities, it may be possible to drive them atdifferent voltages.

An HSAAM electrode can be positively or negatively charged with respectto the non-HSAAM electrode. When the HSAAM electrode is chargedpositively, it attracts, absorbs and holds negative ions. This causesthe pH of the water in the immediately vicinity of the cell to increase,or become more caustic. When the HSAAM electrode is negatively charged,it attracts, absorbs and holds positive ion, thus lowering the pH of thewater, and making it more acidic.

As each HSAAM electrode 22 is bordered on either side by its own pair ofCC electrodes, adjacent deionization cells within the same tank can beused to remove different types of ions. Thus, if a pair of spaced apartinlets or outlets are provided on the bottom or sides of the same tank,the deionization cells proximate to these inlets may be activated suchthat a first set of cells removes ions of a first type, and a second setof cells removes ions of a second type. Similarly, when serpentine fluidflow is desired, the first, upstream set of cells encountered by thefluid may be activated to remove ions of a first type, while a second,downstream set is activated to remove ions of a second type.

In a given tank, a plurality of cells are typically present. In order tocompletely deionize the water in the tank, both negatively andpositively charged HSAAM electrodes should be present. In general,different voltages should be applied to positive and to negative cellsto effect ion removal, and the number of positively and negativelycharged cells may not be the same. This allows positively and negativelycharged HSAAM electrodes to be activated independently and at differentvoltage levels. Varying the plate spacing and applied voltage, mayenable the removal of specific ions from the fluid being treated.

As shown in FIG. 5, multiple tanks may be chained together, the outletof one being connected to the inlet of the next. In such case, thedeionization cells in each tank may be activated in a common manner sothat each tank focuses on the removal of one type of ion. Alternatively,successive tanks may be used to remove ever decreasing amounts of thesame ion.

As shown in FIGS. 6A and 6B, it is possible to have electrodes of onetype angled slightly with respect to the electrodes of the other type.In FIG. 6A, the HSAAM electrodes are shown to be both parallel to oneanother and upright. In contrast, the non-HSAAM carbon cloth electrodeson either side of an HSAAM electrode are angled symmetrically about theHSAAM electrode. In such case, adjacent HSAAM electrodes have theirrespective carbon cloth electrodes angled in a different manner.Similarly, as shown in FIG. 6B, one may have the carbon cloth electrodesstanding upright, while the HSAAM electrodes are angled with respect tothe carbon cloth electrodes. In the configuration of FIG. 6B, the HSAAMelectrodes are still parallel to one another, but are angled withrespect to, say, the base and walls of the tank.

FIG. 7 shows a top view of a tank comprising four deionization cells. Afirst pair of deionization cells having positively charged HSAAM platesare interleaved with a second pair having negatively charged HSAAMplates. The base of the tank, in the region underlying each deionizationcell, is provided with an array of holes. For the positively chargeddeionization cells, these are shown as holes 82, and for the negativelycharged deionization cells, these are shown as holes 84.

The purpose of holes 82, 84 is to allow for the selective removal ofpositive and negative ions collected on the HSAAM plates when the tankis operational. Thus, in those cells having positively charged HSAAMplates, negative ions will collect on the plates. When the cell isregenerated, these ions may be collected through the holes 82.Similarly, during regeneration, the ions collected on the negativelycharged HSAAM plates, may be collected through holes 84. As shown inFIG. 7, holes 82 and 84 have approximately the same size andarrangement. This, however, is not a necessity. For instance, the holesfor the negatively charged ions may be smaller than those for thepositively charged ions. Also, instead of an array of holes arrangedparallel to the HSAAM and non-HSAAM electrodes, the holes may appear inmore irregular patterns, such as a checkerboard or a honeycomb.

As stated above, the HSAAM electrode is formed from a high surface areaabsorptive material. In the present invention, this material is formedby an inventive process which requires three ingredients: resorcinol,formaldehyde and a reinforcer, such as a carbon source. A catalyst mayalso be used to facilitate polymerization of the resorcinol-formaldehyderesin.

Resorcinol comes in many different grades, and can be obtained from anumber of suppliers in pellets, flakes, and other convenient forms. Inthe examples given below, resorcinol in the form suitable for organicchemical formulations, from the Hoechst Celanese Company, was used.

Formaldehyde is available from a variety of suppliers, and also comes indifferent grades and forms. In the examples given below, formaldehyde inform of formalin, which is suitable for dyes, resins and biologicalpreservation, from the Georgia-Pacific Resin, Spectrum Chemical Companywas used.

The carbon source used as reinforcement in the formation of the HSAAMelectrodes can come in different forms. For instance, loose carbonfibers, such as THORNEL® P25 4K 1/4" cut carbon fiber fibers, availablefrom Amoco, have been successfully used to form HSAAM electrodes for usein the present invention. An alternative which has also successfullybeen used is carbon felt, either graphite felt grade wdf 3331060 orcarbon felt VDG 3330500, both available from the National ElectricCarbon Company. In general, a predetermined quantity of any relativelypure carbon source can be used so long as it can either be fullydispersed in a resorcinol-formaldehyde liquor which then sets, or canabsorb a similar quantity of the liquor in a matrix, and then set. It isimportant that the carbon fibers be electrically conductive.

Although the preferred embodiments of the second type of electrode callfor carbon cloth or carbon felt, the important thing is that anon-sacrificial electrical conductor be used. Therefore, such materialsas graphite, gold, platinum, conductive plastics, glassy carbons such asSIGRADUR, available from SGL Carbon Group of St. Mays, Pa., and thelike, may be used in place of the carbon cloth or carbon felt.

Regardless of the reinforcer used, the process of forming the HSAAMelectrodes begins the same way. 4 lbs. of resorcinol solid is added to3.5 liters of formaldehyde, giving approximately a one-to-two molarratio, at room temperature. The quantities stated, of course, may bescaled linearly, either upwards or downwards, to make different totalquantities of this initial mix. This initial mix is mixed for between 30and 90 minutes, or until the resorcinol dissolves.

When the resorcinol completely dissolves, the resulting mixture has anamber to pink color. If this mixture is maintained at or below roomtemperature, i.e, about 72° F. for about 12 to 24 hours afterdissolution of the resorcinol, this color then turns into a milky andopalescent liquor.

A predetermined quantity of a sodium carbonate catalyst is added to ameasured portion of the liquor and the carbon source and liquor arefully combined.

The resulting material is then heated and poured into an 8"×8" mold to athickness of approximately 3/4" where it is allowed to set into a xerogel (consisting of polymerized resorcinol-formaldehyde) block. The moldis placed on level surface at room temperature where the polymerizationreaction is allowed to continue in air as the material turns into a xerogel block. It takes approximately 20 to 60 minutes for the material in amold to solidify at room temperature. As it solidifies, the materialshrinks by about 0.5-1.0% in each dimension, and pulls away from one ormore side walls of the mold. The block can then be removed by simplyturning the mold upside down.

Upon being removed from its mold, each block is allowed to cure andharden at approximately 80°-90° F. in air for about two hours, to ensurecomplete polymerization. Unlike prior art curing techniques, the curingprocess in the present invention does not entail critical point drying(i.e., supercritical drying). This saves considerable time and cost.While curing removes some of the excess liquid, the resulting block isstill a very poor conductor of electricity.

After curing, the blocks are laid flat in an oven and then carbonized.During carbonization, a weight is placed on each block to preventcracking, uneven buckling, and curling of its edges. Carbonization ispreferably done at a temperature of about 1850°-2200° F. Experimentationhas shown, however, that temperatures as low as 1750° F. andcarbonization times between 10-20 minutes are also acceptable, the lowerthe temperature, the longer the carbonization time. Subjecting theblocks to this temperature causes further desiccation and burns off manyof the impurities present in the original ingredients. In the preferredembodiment, carbonization can be carried out in an air environment, asthe thickness of the blocks can withstand some loss of material due toburning. This contrasts with prior art techniques in which a nitrogen orother inert gas atmosphere had to be used to prevent relatively thinblocks from being consumed during carbonization.

Once carbonization is complete, the resulting HSAAM plates can then bemachined and sanded into planar electrodes of a desired shape, size andthickness. Preferably, the electrodes have a sufficient thickness to beself-supporting (e.g., able to withstand their own weight when placed onend). This requires a thickness of about at least 1 mm for a 2"×4"electrode. Plates thinner than this may be formed, but the brittlenessof the material makes such thin plates difficult to handle and severelylimits their capacity to remove and store ions from solution. Ingeneral, the thickness of the plate should be made in proportion totheir surface area, larger plates typically needing to be thicker.Regardless of thickness, after carbonization, the block is a goodconductor of electricity.

The exact details of the step of adding the catalyst and the carbonsource to the liquor can be performed in more than one way, depending onthe type of carbon source used. This step is now considered in furtherdetail.

First, is the case where the THORNEL® carbon fibers are used. Eighthundred milliliters (mls) of the liquor are poured into a blender, alongwith 3 ounces of the aforementioned 1/4 THORNEL® carbon fibers, and 10mls of a 1.0 molar solution of sodium carbonate, which serves as thecatalyst to promote polymerization. This combination is then blended forapproximately 3-5 minutes until the carbon fibers are and liquor arefully combined together. As it is blended in, the carbon fibers arefurther chopped into even smaller pieces. The outcome of this blendingis a viscous, black broth which includes the resorcinol/formaldehydeliquor mixed with the sodium carbonate, and carbon fibers combinedtherewith. The temperature of the broth after the blending step is about90° F. It should be noted here that, although only 800 mls of liquorwere used in this example, the process is scalable. Thus, severalliters, or even more, may be batch processed at the same time.

1600 mls of broth made in this manner are then transferred to astainless steel mixing bowl and the broth is then gradually heated usingan electric table heater. As it is heated, the broth is stirred and itstemperature is closely monitored. In this manner, the temperature of thebroth is allowed to rise over a period of 25 to 45 minutes maintainingthe temperature at approximately 130-140° F., 135° F. being the optimumtemperature.

During the heating process, the temperature of the broth is controlledso that it does not exceed 150° F. causing the polymerization to run outof control. Temperature control can be effected by a number of meanssuch as thermoelectric cells, coils having coolant circulatingtherethrough, and even water baths into which the mixing bowl may belowered. Automatic temperature regulation may also be performed usingany of several well known monitoring and control devices.

The consistency of the broth is also monitored during the heatingprocess. This ensures that the carbon fibers do not clump together orsettle, resulting in unevenly dispersed agglomerations of matted carbonfiber. If this happens, the broth may be placed back in the blender tofurther homogenize its contents.

The broth is maintained at a temperature of approximately 135° F., andis continuously stirred to provide for uniform polymerization. Thistemperature is maintained for about 35 minutes, at which time a slightskin forms on the surface of the broth whenever the broth is not stirredfor a few seconds. As the polymerization continues, the broth thickens,becoming increasingly viscous until it reaches a consistency such thatthe carbon fibers are suspended within the broth as colloidal particles.When this point is reached, the heated broth is poured into an 8"×8"mold to a thickness of approximately 3/4".

It should be noted here that the temperature of the broth when it ispoured should be in the range of 135°-150° F. or so. This helps ensurethat when the broth sets, the resulting solid blocks have isotropicmechanical and electrical properties. When the broth is poured at, orallowed to exceed, temperatures above 150° F., a runaway reaction takesplace, resulting in deformed blocks having boils and other unevensurface and volumetric features. These result in a block with structuraland electrical anisotropy.

The second case is where carbon felt, plain cellulose fiber, orcellulose fiber impregnated with activated carbon is used to reinforcethe resorcinol-formaldehyde resin. The carbon fiber felt, or mat, is cutto fit into the mold. Resorcinol-formaldehyde liquor is then poured intothe mold to cover the carbon felt, thereby displacing air trapped withinthe felt. The mold is then transferred into a curing oven set at 92° F.and allowed to polymerize for approximately 72 hours so as to form axero gel block. The xero gel is then placed in an oven and carbonized atbetween 1850-2200° F. While being carbonized in the oven, the xero gelwas restrained with a force of 0.5-0.8 lbs/in² in the form of refractoryblocks. The oven used for this purpose was an electric muffle furnacehaving a top vent. The result of this carbonization is an HSAAM product.After the HSAAM was removed from the furnace, it was allowed to cool inair. The cooled HSAAM was then machined on a flat sanding wheel to adesired uniform thickness. Finally, this plate was squared utilizing acarbide tipped table saw.

Regardless of the carbon source used, the resulting blocks are black incolor and serve as conductors of electricity.

In the above description, resorcinol is used as one of the ingredients.However, experimentation has shown that suitable blocks can be formedusing one of the following chemicals in place of resorcinol:1,5-dihydroxy naphthalene, 2,3-dihydroxy naphthalene, 1,4-dihydroxynaphthalene and 1,4-dihydroxy benzene. Each of these chemicals was foundto form a polymer with formaldehyde, successfully carbonized into ablock, and subsequently deionized water when a current was applied. Ingeneral, then, it is believed that any dihydroxy or trihydroxy benzeneor naphthalene can be used in place of resorcinol. This is because thesechemicals are similar in chemical structure, share the characteristic offorming a polymer with formaldehyde, and are likely to form carbonizedblocks which can be used in ion removal. Presently, resorcinol ispreferred because of its low cost, its wide availability in largequantities, and its amenability to reacting with formaldehyde at roomtemperature and pressure.

FIG. 8. illustrates an apparatus constructed in accordance with thepresent invention. This apparatus comprises three tanks 102, 104, 106.The three tanks were used in series to deionize city of Pueblo, Colo.sewage effluent. The effluent was introduced at the inlet 108 to thefirst tank 102 and the final product exited the system from outlet 122of tank 106. Overall, the system could deionize up to 1500 millilitersper minute (ml/min).

In this system, tanks 102 and 106 had identical construction. Each wasprovided with six deionization cells. In both tanks, 102, 106, the HSAAMelectrodes in adjacent deionization cells had different polarities. Thisgave a voltage-interleaved deionization arrangement in each tank. As aconsequence, both tanks 102, 106 were arranged to take out both positiveand negative ions. Therefore, each of these tanks had two voltagesources, one voltage source arranged to create positively chargeddeionization cells, and a second voltage source arranged to create anegatively charged deionization cells.

Tank 102 was connected to intermediate tank 104. The partially deionizedeffluent from tank 102 passed through outlet 110, valve 112, inlet 114and on into second tank 104. Although shown as a single inlet, inlet 114was in fact a multiplicity of conduits entering second tank 104. Thepurpose of valve 112 is to interrupt the electrical conduction processbetween tanks 102 and 104. Also, outlet 110 of tank 102 may be providedwith a bleed (not shown) to test the partially deionized effluent toassess the performance of tank 102.

Tank 104 is also provided with six deionization cells. However, thesedeionization cells are of double length. The HSAAM electrodes of eachare provided with a rabbit joint at their ends so that they can matewith a complementary structure on a similar plate. In contrast to tank102, all the deionization cells in tank 104 have positively chargedHSAAM electrodes. This means that only negative ions are removed in tank104.

The further deionized effluent from tank 104 exits through outlet 116,passes through valve 118, enters inlet 120, and from there enters tank106 itself. Outlet 116 may also be provided with a bleed so as to samplethe effluent from tank 104.

As stated above, tank 106 is similar in construction to tank 102. Itfurther deionizes the liquid entering inlet 120. The deionized outputfrom tank 106 exits the system at outlet 122.

In tanks 102 and 106, the HSAAM electrodes were 61/2"×13"×0.4" and wereformed from 2 plates of dimensions 61/2×61/2"×0.4". To form the platesof tanks 102, 106 a 0.25" rabbit joint was cut in one edge and acomplementary joint was cut in an opposing edge from an abutting plate.The two plates were fitted into frames and were glued end to end with aconductive epoxy. For tank 104, four plates were fitted in a similarprocess. For all tanks, electrical connection was made with a carbonfiber wire that was adhesively joined, such as by epoxy, to the clipsmounting the HSAAM plates to the frame.

In tanks 102 and 106, water was introduced into each tank near the topof the HSAAM electrodes at a single point. Once inside the tank, thewater was mixed continuously during deionization. The purpose of mixingis to help prevent the creation of localized acidic or caustic regionsof the tank, during deionization. Mixing can be accomplished by aeratingthe tank at multiple points along the bottom of that tank, althoughother mixing means, such as magnetic or mechanical stirrers and spinnersmay be used instead. The overall retention time of water in a giventank, was determined solely by the flow rate which, as stated above,under 1500 ml/min.

As an alternative to introducing water at a single point in each of thetanks, one may provide multiple inlets in each tank, at one end of theHSAAM and non-HSAAM plates, and multiple outlets at the other end of theplates. In such case, the water would travel the length of adeionization cell before exiting.

Tanks 102 and 106 had voltages applied to them which were dependent onthe conductivity of water being deionized. Applied voltages range from0.01-15 volts during the deionization in these two tanks. Thecorresponding amperage ranges from 0.01-10 amps during deionization. Thedeionization rate of the water (i.e., the rate at which ions wereremoved) was a function of the type of water being deionized. Hence, therate for deionization in tank 102, which had more impurities, wasgreater than that of tank 106, which was treating water that had beentwice deionized.

The second tank, 104 removed negatively charged ions. This resulted inthe water in this tank becoming caustic, thus creating a caustic flock.The second tank was operated in a serpentine flow pattern with the inletbeing placed near the bottom of the HSAAM plates. The voltage andcurrent applied to the water within tank 104 was sufficient to causeelectrolysis of the water. Treatment of water in this second tankresulted in the removal of approximately 300-500 μmho/cm or μS/cm ofconductivity. However, the caustic output from this tank had a pH in therange of 8-12, which then was sent on to the third tank 106.

Table 1 shows the experimental results achieved using the system of FIG.8. In particular, Table 1 shows the effects of each stage ofdeionization using an apparatus formed in accordance with the presentinvention. The values reported in Table 1 indicate that the output fromtank 106 (the last tank) is consistent with potable water, as it meetsthe limitations for Federal water standards.

                  TABLE 1    ______________________________________    Deionization of City of Pueblo, Colorado    Sewage Effluent Using the System of FIG 8.    Parameter Enter System                         Exit 102 Exit 104                                          Exit 106    ______________________________________    Conductivity μS              2000       1300     900     500    pH Range  7.1-7.7    3.3-11.2 10.1-12.4                                          6.6-7.2    Total Hardness              560        492      342     144    mg/l    Total Coliform              over grown 456       5       0    (colonies/100    ml)    Total Alkalinity              280         60       60      10    mg/l    Ammonia mg/l)                17.1      12       6       4    Total Dissolved              1188       781      540     300    Solids mg/l    Sulfates mg/l              840        830      423     400    Chloride mg/l               28         10       8       3    Odor      strong     mild     absent  absent    Color     clear green                         clear    clear   clear                         green    colorless                                          colorless    ______________________________________

Table 2 shows the experimental results achieved using the system of FIG.8. In particular, Table 2 shows the effects of each stage ofdeionization using an apparatus formed in accordance with the presentinvention.

                  TABLE 2    ______________________________________    Treated Super Fund Site of Yak Tunnel/California    Gulch operated by Asarco, Inc. near Leadville,    Colorado, deionization results of the system of FIG. 8.    Parameter Enter System                          Exit 102 Exit 104                                          Exit 106    ______________________________________    Conductivity μS              1240        860      680    300    pH range  3.2-4.2     7.1-7.6  8.6-11.1                                          7.1-7.7    Color     opaque/orange                          clear    clear/ clear/                          orange   colorless                                          colorless    Total Arsenic               2          not      >mdl   >mdl    μg/l               tested    Total Cadmium              137         not      100      45.7    μg/l               tested    Total Copper               40         not       25    11    μg/l               tested    Total Iron μg/l              4060        not      456    176                          tested    Total Lead μg/l               8          not      >mdl   >mdl                          tested    Total Manganese              13800       not      5370   2970    μg/l               tested    Total Zinc μg/l              38600       not      23000  11400                          tested    Total Hardness              980         376       64    34    mg/l    Total      0           70      176    72    Alkalinity mg/l    Sulfate mg/l              778         414      231      39.8    Chloride mg/l                16.7         4.8      4.8   5.8    Calcium   240         276       64    34    Hardness mg/l    Magnesium 740         100      >mdl   >mdl    Hardness mg/l    ______________________________________

In addition to continuous flow deionization, the apparatus can also beused for batch process deionization. Results of batch processing aregiven by FIGS. 9A-9E. In particular, these figures show the results ofdeionizing a batch of water spiked with known concentrations of iron,sodium, and copper ions. Iron and copper ions were removed to a levelbelow 1 part per billion, sodium ions were removed to a level below 2parts per million, and conductivity was reduced from 12,150 μS to 410μS.

The pH and conductivity level of the water in each of the three tankswas monitored to establish when the HSAAM plates were saturated. A risein the conductivity of the water outflow without a corresponding changein the pH indicates that the HSAAM plates were saturated with ions andthat the apparatus needs to be regenerated. Similarly, stored charge inconjunction with pH & conductivity in the cell can be used to indicatewhen the apparatus needs to be regenerated. In general, HSAAM platesbecome discolored as they deionize the water. The type and color ofchange depends on the type of water being treated. For instance, waterhaving high sulfate levels causes the plates to turn white as thesulfate is deposited on them. Similarly, water having high organic wastecontent causes the HSAAM plates to turn to a brown color. Either way,this discoloration indicates that regeneration is necessary due to ionsaturation levels.

With tanks 102 and 106, it was possible to either form an oxidized flockor a concentrated ion solution during regeneration. Whether one or theother was created, depended upon the voltage level applied. Applying avoltage lower than that necessary to cause the electrolysis of water,allowed one to collect the ion rich water from the negatively orpositively charged deionization cells via the bottom holes 82, 84, asshown in FIG. 7. On the other hand, applying a voltage sufficient toelectrolyze the water, resulted in the formation of an oxidized flock.In such case, mixing was required during regeneration to produce anddischarge this flock from the tank.

In the second tank, 104, negatively charged ions were removed. Thisresulted in the water becoming caustic, resulting in a pH on the orderof 8-12. This also resulted in the formation of a caustic flock. Duringoperation, the voltage applied to the deionization cells in tank 104 wassufficient to cause electrolysis of water. Thus, the voltage applied wason the order of 1 to 12 volts with an amperage of between 1.3-12 amps.The effect of this was that the second tank, 104, caused the removal of300-500 μmho/cm or μS/cm of conductivity.

Regeneration of the plates in the second tank, 104, was conducted byreversing the current applied to the plates with enough voltage toovercome the cells' stored charge (counter EMF). Again, a rise in theconductivity of water outflow without a change in pH, indicated that theHSAAM's in the second tank 104 were saturated with ions, signifying thatthe apparatus needed to be regenerated. This could most easily bediscerned by the fact that the HSAAM plates became severely discolored,the type and color of change depending on the type of water beingcleaned. During regeneration, an oxidized flock was produced byoperating the device at a voltage needed to counter the EMF that hadbuilt up during the operation of the system.

These flocks could then be collected through the holes in the bottom ofthe tank 104. After regeneration, all three tanks 102, 104, 106 can thenbe reused with the same efficacy as before.

The power supplies used to supply the necessary voltages fordeionization preferably can be controlled over a finite range ofvoltages. Typically, then, the power supplies will be of the type thatcan be plugged into an AC outlet. However, as fairly low voltages andcurrents are needed, portable, battery-powered power supplies may beused in certain settings. In this vein, a solar-powered deionizationapparatus has been constructed and successfully operated, albeit at alow throughput. Solar-powered and battery-powered systems of reducedsize provide the dual advantages of low cost and high portability.

FIG. 10 shows an overview of an automated deionization control system130 in accordance with the present invention. The system monitors thewater quality to automatically adjust the voltages to achieve a targetrate of deionization. As shown in this figure, the system 130 controlsthe operation of two tanks 132, 134. It should be kept in mind, however,that a control system could also be used with either a single tank, orwith three or more tanks, be they connected in serial, or in parallel,or in a combination of the two.

The control system uses sensor modules 138, which monitor the effluentat various stages in the deionization plant. These sensor modules 138comprises one or more sensors configured to gauge such properties as pH,conductivity, water flow rate, temperature, optical characteristics,etc., of the effluent. The sensor modules may also include ion-specificprobes, such as those measuring fluoride, ammonia, chloride and others,such as those listed in Tables 1 & 2. The sensors may sample theeffluent continuously, at predetermined periodic intervals, or uponrequest from the controller 136. While in the preferred embodiment, thesensors are shown to sample the effluent in the piping connecting to atank, the sensors may be placed inside a tank, as well.

The sensors data is presented to a programmed logic controller 136. Thecontroller may be implemented as a microprocessor, or equivalent. Thecontroller 136 assesses the performance of the tanks 132, 134 based onthe sensor data. The controller uses these data to determine whether anychanges in the flow rate and the flow pattern should be made. If so, thecontroller outputs signals to motor-driven valves 140 to adjust the flowrate. These valves may be controlled either simultaneously, orindividually. In cases where there are multiple inlets or multipleoutlets, it may be possible to control only a subset of these so as toensure no overflow of any of the tanks.

In addition to selectively controlling the flow rate, the controller 136also controls the voltages applied by the various power supplies, showngenerally as 142. In particular, the controller processes the sensordata and outputs control signals to the power supplies, to therebycontrol the voltages and/or currents applied to the deionization cellsin the tank. The controller 136 uses the sensor data to determinewhether the electrodes in the tank need to be regenerated and, if so,outputs the appropriate signals to the power supplies to effect this.

A control system as described above may be useful in a large scaledeionization apparatus capable of handling flow rates on the order ofseveral thousands of gallons per hour. Thus, such an apparatus may bescaled up to serve the deionization needs of industrial plants, citywater and sewage treatment plants, and the like. Experimental resultshave shown that the electrode dimensions and the number of electrodescan be increased linearly without significantly impacting either thevoltage applied or the current drawn.

It should be noted that the apparatus of the present invention does not,strictly speaking, perform capacitive deionization in that the non-HSAAM(non-absorptive) electrodes never actually store a charge. Indeed, ionsare never deposited on these electrodes, regardless of how theseelectrodes are charged; only the HSAAM electrodes ever trap and storeions.

It should also be noted that the foregoing preferred embodiments teachthe formation and use of planar electrodes. However, alternate electrodeand deionization cell geometries may also be used. One such example isan annular deionization cell comprising 1) an solid or annular innernon-HSAAM electrode, 2) an annular HSAAM electrode concentric with theinner non-HSAAM electrode, and 3) an annular outer non-HSAAM electrode,concentric with the first two electrodes. Such an arrangement wouldallow for fluid flow between the annular HSAAM electrode and the twonon-HSAAM electrodes. However, in such an arrangement, the inner andouter non-HSAAM electrodes would have different surface areas facing theHSAAM electrode. Therefore, it may be necessary to use either differentvoltages or currents between the two non-HSAAM electrodes and the HSAAMelectrode sandwiched between the two.

While the present invention has been disclosed with reference to certainpreferred embodiments, these should not be considered to limit thepresent invention. One skilled in the art will readily recognize thatvariations of these embodiments are possible, each falling within thescope of the invention, as set forth in the claims below.

What is claimed is:
 1. A non-sacrificial absorptive electrode comprising:at least one from the group consisting of dihydroxy benzenes, trihydroxy benzenes, dihydroxy naphthalenes and trihydroxy naphthalenes; formaldehyde; a carbon reinforcing agent; a catalyst; or reaction products thereof, together in a carbonized form, wherein said electrode has a thickness greater than 3 mm and the carbon reinforcing agent is substantially dispersed throughout said thickness.
 2. The electrode of claim 1, wherein:said one from the group consisting of dihydroxy benzenes, trihydroxy benzenes, dihydroxy naphthalenes and trihydroxy naphthalenes is resorcinol.
 3. The electrode of claim 2, wherein:said carbon reinforcing agent is at least one from the group consisting of carbon fiber, carbon felt and cellulose.
 4. A liquid deionizing apparatus comprising:a first tank member having at least one opening for the entry of said liquid; a plurality of spaced apart non-sacrificial absorptive electrodes of a first type positioned in said first tank member, each of said electrodes of a first type having a pair of side surfaces facing in different directions; a plurality of non-sacrificial electrodes of a second type positioned on either side of each of said electrodes of a first type, said electrodes of a second type having a different composition than the electrodes of a first type; and a first voltage source arranged to apply a first voltage differential between at least a first electrode of a first type and a corresponding pair of electrodes of a second type on either side of said first electrode of a first type; wherein said electrodes of a first type comprise:at least one from the group consisting of dihydroxy benzenes, trihydroxy benzenes, dihydroxy naphthalenes and trihydroxy naphthalenes; formaldehyde; a carbon reinforcing agent; a catalyst; or reaction products thereof, together in a carbonized form, said electrodes of the first type having a thickness of at least 1 mm.
 5. The apparatus of claim 4, wherein said electrode of a second type is one from the group consisting of carbon cloth, carbon felt, graphite, gold, platinum, conductive plastic and a glassy carbon.
 6. The apparatus of claim 4, further comprising mixing means placed in the tank and arranged to mix a liquid being deionized in the tank.
 7. The apparatus of claim 4, where the mixing means comprises an aerator placed along an inside bottom surface of the tank, said aerator arranged to introduce a gas into the liquid.
 8. The apparatus of claim 4, wherein the electrodes of a first type are slanted at an angle relative to the electrodes of a second type, in the first tank member.
 9. The apparatus of claim 4 whereinat least one electrode of a second type is affixed to each of oppositely facing first and second sides of a substantially flat, non-conductive structural support member, the electrode of the second type on the first side of said structural support member being electrically isolated from the electrode of the second type on the second side of said structural support member, and said structural support member with said electrodes of the second type mounted thereon being positioned between two electrodes of the first type.
 10. A liquid deionizing apparatus comprising:a first tank member having at least one opening for the entry of said liquid; a plurality of spaced apart non-sacrificial absorptive electrodes of a first type positioned in said first tank member, each of said electrodes of a first type having a pair of side surfaces facing in different directions; a plurality of non-sacrificial electrodes of a second type positioned on either side of each of said electrodes of a first type; and a first voltage source arranged to apply a first voltage differential between at least a first electrode of a first type and a corresponding pair of electrodes of a second type on either side of said first electrode of a first type; and a plurality of holes placed on a bottom member of the first tank member between said spaced apart electrodes of a first type, said holes being sized to accommodate the removal of a solid flock, when a polarity of the first voltage differential is reversed, wherein at least one electrode of a second type is affixed to each of oppositely facing first and second sides of a substantially flat, non-conductive structural support member, the electrode of the second type on the first side of said structural support member being electrically isolated from the electrode of the second type on the second side of said structural support member, and said structural support member with said electrodes of the second type mounted thereon being positioned between two electrodes of the first type, and wherein said electrodes of a first type comprise:at least one from the group consisting of dihydroxy benzenes, trihydroxy benzenes, dihydroxy naphthalenes and trihydroxy naphthalenes; formaldehyde; a carbon reinforcing agent; a catalyst; or reaction products thereof, together in a carbonized form, said electrodes of the first type having a thickness of at least 1 mm.
 11. The apparatus of claim 10, further comprising mixing means placed in the tank and arranged to mix a liquid being deionized in the tank.
 12. The apparatus of claim 11, where the mixing means comprises an aerator placed along an inside bottom surface of the tank, said aerator arranged to introduce a gas into the liquid.
 13. A liquid deionizing apparatus comprising:a first tank member having at least one opening for the entry of said liquid; a plurality of spaced apart non-sacrificial absorptive electrodes of a first type positioned in said first tank member, each of said electrodes of a first type having a pair of side surfaces facing in different directions; a plurality of non-sacrificial electrodes of a second type positioned on either side of each of said electrodes of a first type, said electrodes of a second type having a different composition than the electrodes of a first type; a first voltage source arranged to apply a first voltage differential between at least a first electrode of a first type and a corresponding pair of electrodes of a second type an either side of said first electrode of a first type; and a second voltage source arranged to apply a second voltage differential between a second electrode of a first type, and a corresponding pair of electrodes of a second type positioned on either side of said second electrode of a first type, in the first tank member.
 14. The apparatus of claim 13, wherein the first and second voltage differentials have different polarities.
 15. The apparatus of claim 13, further comprisinga second tank member having an inlet connected to an outlet of said first tank member; and a third voltage source arranged to provide a third voltage differential between at least a first electrode of a first type in the second tank, and a corresponding pair of electrodes of a second type on either side of said first electrode of a first type, in the second tank member.
 16. The apparatus of claim 15, further comprisinga fourth voltage source arranged to provide a fourth voltage differential between at least a second electrode of a first type in the second tank, and a corresponding pair of electrodes of a second type on either side of said first electrode of a first type, in the second tank member.
 17. The apparatus of claim 16, wherein the first and second voltage differentials have different polarities, and the third and fourth voltage differentials have different polarities.
 18. The apparatus of claim 16 further comprisinga third tank member having an inlet connected to an outlet of the second tank member; and a fifth voltage source arranged to provide a fifth voltage differential between at least a first electrode of a first type in the third tank, and a corresponding pair of electrodes of a second type on either side of said first electrode of a first type, in the third tank.
 19. The apparatus of claim 18, further comprising aa sixth voltage source arranged to provide a sixth voltage differential between at least a second electrode of a first type in the third tank, and a corresponding pair of electrodes of a second type on either side of said first electrode of a first type, in the third tank member.
 20. The apparatus of claim 19, wherein the first and second voltage differentials have different polarities, the third and fourth voltage differentials have different polarities, and the fifth and sixth voltage differentials have different polarities.
 21. The apparatus of claim 13 whereinat least one electrode of a second type is affixed to each of oppositely facing first and second sides of a substantially flat, non-conductive structural support member, the electrode of the second type on the first side of said structural support member being electrically isolated from the electrode of the second type on the second side of said structural support member, and said structural support member with said electrodes of the second type mounted thereon being positioned between two electrodes of the first type.
 22. The apparatus of claim 21, wherein said electrodes of a first type comprise:at least one from the group consisting of dihydroxy benzenes, trihydroxy benzenes, dihydroxy naphthalenes and trihydroxy naphthalenes; formaldehyde; a carbon reinforcing agent; a catalyst; or reaction products thereof, together in a carbonized form, said electrodes of a first type having a thickness of at least 1 mm.
 23. The apparatus of claim 22, wherein said electrode of a second type is one from the group consisting of carbon cloth, carbon felt, graphite, gold, platinum, conductive plastic and glassy carbon.
 24. The apparatus of claim 13, further comprising:at least a first sensor arranged to measure a property of the liquid being treated and output a first data signal reflective of said property; and a controller receiving said first data signal and outputing a first control signal in response thereto, said first control signal adjusting at least one of said first and second voltage differentials applied by respective said first and second voltage sources.
 25. The apparatus of claim 24, further comprising a valve controlling a flow rate of liquid into said first tank, wherein said controller outputs a second control signal which adjusts a position of said valve such that said flow rate is affected. 